1. Field of the Invention
The invention relates to transition metal-based olefin polymerization Ziegler-Natta catalysts, methods of making the same and methods of using the same.
2. Description of Related Art
Several publications are referenced in this application. These references describe the state of the art to which this invention pertains, and are incorporated herein by reference.
In the field of olefin catalysis, there have been many remarkable discoveries during the last 50 years. In particular, two broad areas of invention stand out. Firstly, in the 1950""s, the Ziegler or Ziegler-Natta type catalysts were discovered and exploited for a variety of applications. Today, these catalyst systems, most often referred to as Ziegler-Natta catalysts, are used extensively in commercially important industrial operations. Secondly, and more recently, the discovery of xe2x80x9cMetallocenexe2x80x9d catalysts having cyclopentadieneyl-modified transition metal complexes has advanced polyolefins research and commercialization.
However, despite the progress in these areas, there are still certain limitations as recognized by those of ordinary skill in the art. For example, traditional Ziegler-Natta catalysts (hereafter referred to as Z-N catalysts) often display limited productivity, where productivity is defined as the efficiency of conversion of monomer to useful polymer per unit of transition metal catalyst utilized.
In contrast, metallocene-based catalysts intrinsically possess high rates of productivity. Typically, however, commercial plants are not able to use such high levels of productivity and refitting such plants would be prohibitively expensive. That is, many commercial plants are not able to use such high levels of productivity because the amount of polymer is in excess of the downstream equipment""s ability to process the product. Additionally, the resultant polymers often have undesirable physical characteristics such as very low bulk density and a very narrow molecular weight distribution. These factors, among others, may be seen to negatively impact the commercial utility of these metallocene-based catalyst materials.
To overcome these limitations, the so-called metallocene catalyst systems have often been modified by incorporating the catalysts with non-metallocene catalyst systems thus yielding commercial polymers having an acceptable balance of properties. However, preparing such multi-component catalysts is cumbersome and expensive.
U.S. Pat. Nos. 4,701,423 and 5,183,867 to Welborn, Jr., et al., describe supported olefin polymerization catalysts and processes of using the same. These catalysts may contain at least one metallocene compound of a metal of Group IVB, VB, and VIB of the Periodic Table, a non-metallocene transition metal containing compound of Group IVB, VB, or VIB metal and an alumoxane. The catalysts are reaction products formed in the presence of a support. Welborn describes the utility of the catalysts for the polymerization of olefins, especially ethylene and especially for the copolymerization of ethylene and other mono- and diolefins. More specifically, the Welborn ""423 patent describes supported olefin catalyst systems wherein the catalyst components consist of a metallocene, a nonmetallocene transition metal component, an alumoxane and optionally, a cocatalyst system of an organic compound of a metal of Groups I-III of the Periodic Table, particularly, those known in the art as aluminum alkyls. The Welborn ""867 Patent also relates to the use of a two component transition metal complex wherein alumoxane and, optionally, aluminum alkyls are used to prepare polymers having multimodal molecular weight distributions (MWD).
U.S. Pat. No. 4,303,771 to Wagner, et al., relates to a catalytic process for preparing ethylene polymers having a density ranging from greater than or equal to 0.94 to less than 0.97 g/cm3 and a melt flow rate of about 22 to about 32 in a low pressure reactor at a productivity of greater than or equal to 50,000 lbs of polymer per pound of titanium with a catalyst formed from selected organoaluminum compounds and a precursor composition being the reaction product of titanium trichloride, magnesium dichloride and an electron donor (ED) compound such as tetrahydrofuran in specific ratios. This precursor is used as a xe2x80x9cpartially activatingxe2x80x9d compound before being introduced into a polymerization reactor.
U.S. Pat. No. 4,302,566 to Karol, et al., also relates to the preparation of transition metal catalysts supported on an inert carrier material and reacted with selected organoaluminum compounds. Additionally, the Karol ""566 patent relates to specific activation sequences for the catalytic entities.
U.S. Pat. No. 4,124,532 to Giannini, et al., describes the usefulness of incorporating various alkali and alkali earth metal complexes, e.g., magnesium dichloride, into olefinic transition metal polymerization catalysts. These compounds are disclosed as having a positive effect on the activity of the polymerization of ethylene and alpha-olefins while generally being much less active than the corresponding transition metal halides.
In view of the prior art limitations, it would be useful to provide methods of producing homo- and copolyolefin polymers with catalysts which overcome the above-described stated limitations of the conventional catalyst systems. In particular, it would be useful to provide for increased productivity while concomitantly broadening the molecular weight distribution while maintaining relatively consistent values of bulk density. These advantages would be recognizable to those of ordinary skill in the catalyst and polymerization arts as commercially valuable. An improvement in productivity means that less catalyst is more economically consumed resulting in a cost savings in the amount of catalyst used to produce a given quantity of polymer.
Additionally, as with most industrial polymers, there are differences between the desired material properties and those which result from a typical production operation. Accordingly, it would also be desirable to positively affect the productivity of the catalyst while minimizing changes in the bulk density of the materials produced. This is particularly true since bulk density significantly affects the commercial aspects of polymers, e.g., the shipping of and handling of the polymer materials.
Therefore, it would be advantageous to have a catalyst system having a productivity typically higher than traditional Z-N systems, but without the inherent tradeoffs including the narrowing of the molecular weight distribution and the decrease in the bulk density which occur with metallocene catalysts systems. Thus, a second useful advantage in an olefinic catalyst system would be improving the physical properties of the polymers produced (especially a wide molecular weight distribution) while maintaining a constant value for the bulk density. A polyolefin having these characteristics would be more suitable for different kinds of processing operations (e.g., molding) and particularly, injection molding and film fabrications operations. Still another advantage in an olefinic catalyst system would be the significantly increased flexibility in preparing various combinations of cocatalyst systems useful for polymerization of olefins monomers.
It is an object of the invention to overcome the above-identified deficiencies.
It is another object of the invention to provide a catalyst for use in olefin polymerizations having a useful, improved range of productivity and methods of using the same.
It is a further object of the invention to provide a method of making improved catalysts for use in olefin polymerizations.
It is a still further object of the invention to provide methods of making improved polymer products from olefin polymerizations having improved physical properties including improved molecular weight distributions, single melting point peak, and/or improved bulk density.
The foregoing and other objects and advantages of the invention will be set forth in or apparent from the following description.
The inventors of the present application have surprisingly and unexpectedly discovered a process for the in-situ preparation of an alumoxane-modified transition metal based catalyst system which when used for the polymerization of olefinic monomers (particularly ethylene, and copolymers with propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl pentene) displays catalytic productivity significantly higher than other similar catalyst systems. According to one preferred embodiment of the invention, the activity or productivity may be increased by a factor of at least 100% compared with other known (comparative) catalyst systems.
The inventors have unexpectedly and surprisingly found that in situ-activation of a Ziegler-Natta-type catalyst precursor with either an alumoxane or an alumoxane combined in specific ratios with conventional aluminum alkyls, which is subsequently completely activated in the polymerization reactor, yields enhanced polymerization productivity. The catalyst systems of the invention also reduce the amount of expensive alumoxane used in the polymerization. This inventive process is useful in the polymerization of olefin monomers, particularly ethylene and other useful comonomers, having a single melting point peak, a useful, broad range of molecular weights, and melt flow rates (MFR""s) providing useful polymers having desirable characteristics as recognized and taught by those of ordinary skill in the art.
One aspect of the invention relates to improved polymerization catalysts. The supported transition metal based catalyst systems of the present invention are preferably obtained by preparing a precursor which is the reaction product of a mixture of at least one transition metal compound, at least one alkali earth halide or alkali metal halide complex and at least one non-transition metal electron donor (preferably, a weakly coordinating electron donor) in an effective amount of a hydrocarbon liquid, while heating said mixture over a temperature range of from about 60xc2x0 C. to 75xc2x0 C., while refluxing said mixture under an inert atmosphere to form a catalyst precursor, and depositing the precursor on an inorganic support and pre-activating the precursor with an alumoxane(s) or an alumoxane(s) with aluminum alkyls. Subsequently, the pre-activated catalyst component is fully activated in situ before polymerization using alumoxanes.
Suitable support materials include silica, alumina, silica-alumina compounds and mixtures thereof as known by those skilled in the art. Other suitable support materials may also be employed, for example, finely divided polyethylene, polypropylene or polystyrene and the like.
According to one embodiment, a silica support is used. The silica support is preferably substantially dehydrated to minimize the surface hydroxyl groups and thus make the support inert towards the catalyst precursor. Such treatments as known to those of ordinary skill in the art may be carried out in vacuum or while fluidizing with an inert gas such as nitrogen or argon and the like at a temperature between about 200xc2x0 C. to 1000xc2x0 C., preferably, from 400xc2x0 C. to 600xc2x0 C. The duration of such thermal treatment may be anywhere from 2 to 16 hours.
To control the catalyst activity and thus the resulting polymer bulk properties, chemical modification of the support material with organomagnesium and/or organoaluminum compounds such as alkyl aluminums or alkyl magnesium may be suitably employed. A ratio of from about 2 to 10 weight percent of these surface-modifying agents can be used. Pretreatment may be carried out at a temperature from 30xc2x0 C. to 120xc2x0 C., preferably 40xc2x0 C. to 60xc2x0 C., for 2 to 8 hours. Suitable low boiling point hydrocarbon diluents include hexane, heptane, isopentane and the like as a slurry medium to accomplish such treatments.
The inventive catalyst systems contain at least one transition metal. Illustrative but non-limiting examples of useful transition metal compounds include TiCl3, TiCl4, Ti(OC2H5)3Cl, VOCl3, VCl4, ZrCl4, ZrCl3(OC2H5) and the like as useful in the various embodiments of the present invention. However, Ti-containing compounds are preferred and titanium trichloride is the most preferred.
Alkali earth or alkali metal halide compounds are used in the catalyst systems as substrates that dilute titanium centers (and hence increase the active centers), stabilize active titanium centers from the deactivation process, and enhance the chain transfer process during polymerization. Magnesium halide is the preferred alkali earth halide. Examples of the magnesium halide compounds useful in the present invention include MgCl2 and MgBr2. MgCl2 is the more preferred compound, especially anhydrous MgCl2. Preferably, approximately 1 to 10 moles of magnesium chloride per mole of the titanium compound are used. Other suitable alkali earth compounds include Mg(OR)2 or Mg(OH)Cl, where R is an alkyl group.
The inventive catalyst systems also contain at least one non-transition metal electron donor. Illustrative but non-limiting examples of electron donor compounds, known as xe2x80x9cLewis Bases,xe2x80x9d include aliphatic and aromatic esters, aliphatic ethers, cyclic ethers, and aliphatic ketones. The preferred compounds include tetrahydrofuran, dioxane, acetone, methyl formate and diethyl ether. The most preferred electron donor compound is tetrahydrofuran. The molar ratio of the electron donor compound to the titanium compound ranges from about 2 to 30 moles, and more preferable from about 5 to 15 moles of the electron donor compound per mole of the titanium compound.
In order to influence the morphology of polymers prepared using embodiments of the present invention, in particular the bulk density of the polymers, the supported catalyst precursors are pre-activated with an alumoxane and/or various bulky aluminum alkyls at an activator to titanium molar ratio of from about 0.1 to about 15, more preferably about 0.1 to 10. Pre-activation is achieved using a hydrocarbon slurry medium typically at temperatures from about 15xc2x0 C. to 30xc2x0 C. with continuous mixing followed by drying at temperatures between about 30xc2x0 C. to 100xc2x0 C., and preferably about 50xc2x0 C. to 80xc2x0 C., to obtain a free-flowing solid. Illustrative but non-limiting examples of the pre-activating agents include diethyl aluminum chloride (DEAC), trihexyl aluminum (TnHAL), trioctyl aluminum (TnOCTAL), methyl aluminoxane (MAO), and mixtures thereof.
Activation of the pre-activated catalyst precursor, prior to polymerization, is accomplished by feeding a slurry of the pre-activated precursor into a suitable reactor under a nitrogen atmosphere, typically in an inert hydrocarbon diluent such as hexane, heptane, isopentane, toluene, mineral oil or other hydrocarbons known to be useful in the field, followed by the addition of an alumoxane-based cocatalyst. A cocatalyst is diluted with from about 2 to 40 weight percent of a hydrocarbon solvent similar to the one used to slurry the preactivated catalyst, and is subsequently added to the reactor as a solution. Preferably, the total molar ratio of aluminum to titanium in the system is 5 to 300, preferably about 100 to about 250, and more preferably 50 to 150 depending on the specific embodiment. Illustrative but non-limiting examples of the cocatalyst systems employed in the present invention include, but are not limited to, physical mixtures of alumoxane including polymeric methyl aluminoxane (MAO), co-polymeric isobutyl methyl aluminoxane (CoMAO), and mixtures of MAO or CoMAO along with conventional trialkyl aluminum compounds, such as triethyl aluminum (TEAL), tri-isobutyl aluminum (TIBA), trimethyl aluminum (TMA), trihexyl aluminum, diethyl aluminum chloride and mixtures thereof, said physical mixtures of alumoxane and trialkyl aluminum compounds comprising 10 to 90 mole percent alumoxane, and preferably 10 to 50 mole percent alumoxane, wherein the mole percent corresponds to the molar ratios of aluminum from each compound.
The polymerizations according to the invention may be conducted in slurry or gas phase, as known to those skilled in the art. These polymerizations may be conducted over a temperature range of 30 to 120xc2x0 C., and more particularly between 40 and 100xc2x0 C. According to one preferred embodiment, the polymerization reactor is a gas phase reactor having an internal temperature between 30xc2x0 C. to 115xc2x0 C. at a total reactor pressure ranging between 150 to 1000 PSI. The catalysts of the present invention may be supported catalysts, typically using silica or aluminum, wherein the surfaces of these supports may or may not have been suitably modified as known to those of ordinary skill in the related art. Finally, the process of the present invention may be flexibly practiced using a variety of concentrations of each of the components. The polymers produced using the present invention possess a single melting point peak and/or a useful, broad range of molecular weights, molecular weight distributions (MWD) and MFRs.
The polymerization reaction is carried out by introducing olefinic monomer(s), comonomers and hydrogen into a reactor. Preferably, the reaction temperature is between 50xc2x0 C. to 110xc2x0 C., most preferably 70xc2x0 C. to 90xc2x0 C. Preferably, the total reactor pressure is 5 to 30 bar, more preferably 7 to 20 bar. After polymerization and deactivation of the catalyst, polymer is recovered, washed and dried in a vacuum oven.
An embodiment typical of the present invention will have a productivity of from 125,000 grams or more of polymer produced per gram of titanium in the catalyst. Typically, the molecular weight of a polyethylene homopolymer prepared in accordance with the present invention may vary over a range of from 1,000 to 600,000 grams/mole. The polydisparity index (molecular weight distribution) expressed as Mw/Mn typically varies from 2.5 to 10. The molecular weight and molecular weight distribution are dependent on hydrogen concentration, catalyst systems and the polymerization temperature used.
The polymer density obtained typically varies from about 0.91 g/cm3 to 0.97 g/cm3, depending on the particular embodiment of catalyst, monomer and reaction conditions selected. The polymers produced have a bulk density of from about 0.30 g/cm3 to 0.43 g/cm3 and preferably from 0.37 g/cm3 to 0.42 g/cm3, again, depending on the particular embodiment of supported catalyst, reaction conditions and monomer.